Polymers of dialkylamino aryl itaconamides



United States Patent POLYMERS F DIALKYLAMINO ARYL ITACONAMIDES Gaetano F. DAlelio, Pittsburgh, Pa., assignor to Koppers Company, Inc., a corporation of Delaware No Drawing. Application August 31, 1951, Serial No. 244,692

20 Claims. (Cl. 260-78) This invention relates to new monomers and to new polymeric materials and is particularly directed to the polymerization products obtained by polymerizing a mass comprising as a new monomer an N-(dialkylamino aryl) itaconic acid amide in the presence or absence of other ethylenic copolymerizable compounds especially acrylonitrile. The invention also relates to compositions of these polymerization products adapted to the formation of shaped articles, in many cases to molecularly oriented shaped articles, particularly to fibers, threads, bristles, mono-filaments, etc, hereinafter referred to as fibers, and other shaped articles such as films and the like, which articles show improved dyeing properties.

It has been known for some time that certain copolyroots of acrylonitrile maybe adapted'to the preparation of shaped articles, such as films, fibers, foils, tubes, etc. Some of these copolymers have been regarded as capable of being. cold-drawn to produce structures molecularly oriented along the fiber axis. Cold-drawing may be defined as the stretching of a polymeric material at a temperature below the melting point of the material to give a molecularly oriented structure.

The resistance of acrylonitrile polymers to dyes of all types has presented serious dyeing problems, especially in the development of synthetic fibers from these polymers. In fact, in order to dye polyacrylonitrile one commercial process resorts to the use of high pressures with water solutions or organic dispersions of dyes. It has been proposed that improvement in dye susceptibility can be obtained by the use of itaconic acid in small amounts as copolymerizing monomer in the preparation of acrylonitrile polymers. However, the polymer products obtained thereby have a tendency to crosslink upon standing at temperatures of at least about 70-80" C. or upon spinning from hot solutions. Such crosslinking causes spoilation of material by gelation during storage, embrittlement of fibers, fouling of spinning jets, and other production difiiculties.

In accordance with the present invention it has now been found that crosslinking may be avoided and that improvements in dyeing properties of acrylonitrile polymers are obtained by the polymerization of monomeric masses comprising acrylonitrile and an N-(dialkylamino.

amides can be polymerized per se to form useful polymers. Thus it has been found that valuable polymerization products may be prepared in accordance with the lnvention by polymerizing a monomeric mass compris ing an N-(dialkylamino aryl) itaconic acid amide either in the presence or absence of other ethylenic copolymerizable compounds such as acrylonitrile and the other copolymerizable ethylenic compounds listed hereinafter.

The N-(dialkylamino aryl) itaconic acid amides used in ghe .invention may be represented by the general forum 21 [CHz==C--C,O' Y CH2CO -.Z in which Y is selected from the class consisting of the It has been found still. further that the N-(dialkylamino aryl) itacoriic acid 2,699,436 Patented Jan. 11, 1955 radical Z and the radicals 'RO- and RzN- in which R is selected from the class consisting of hydrogen and the alkyl, aryl, aralkyl, alkaryl, and cycloaliphatic groups which may have halogen-, acyloXy-, or alkoxy-substituents, and when Y is R2N the Rs may be linked together to form with the nitrogen a heterocyclic group and Z is the group R! -I T-A-NR2 in which R is selected from the class consisting of hydrogen and an alkyl group; the radical -NR2" is a dialkylamino group; and A is an aryl nucleus such as benzene or naphthalene. The alkyl groups may be methyl, ethyl, isopropyl, n-butyl, sec-butyl, amyl, hexyl, decyl and the like. Preferably the alkyl groups do not contain more than 3 carbon atoms and the aryl nucleus is unsubstituted except for hydrocarbon substituents containing a total of not more than 4 carbon atoms.

When the amides used in the practice of the invention contain an ester group or an amide group other than group Z, the radical R may be methyl, ethyl, propyl, isobenzyl, phenethyl, phenyl-propyl, phenyl-butyl, acetoXy-' ethyl, 'chlorophenoxyethyl, acetoxy-propyl, acetoXy-isopropyl, acetoxy-phenyl, acetoXy-benzyl, acetoXy-tolyl,

acetoxy cyclohexyl, methoxy propyl, methoxy phenyl,

methoxy-benzyl, methoXy-tolyl, methoxy-cyclohexyl, etc. or part of a heterocyclic amino group, such as, the piperidyl, piperazino and morpholino groups.

The amides set forth above may be formed by reacting amide-forming N-(dialkylamino aryl) amines, i. e., N-(dialkylamino aryl) amines having a replaceable N hydrogen with itaconic acid, itaconic acid anhydride, itaconic acid mono esters, itaconic acid monoamides, and itaconic acid chloride. Since itaconic acid is dibasic, one of the carboxyl groups can be esterified before the amidation. Another amide group similarly can be introduced before the amidation instead of an ester group. Otherwise the amidation may be carried either to the monoor di-amide'stages. If carried to the monostage only, the remaining carboxylic acid group may then be esterified or amidated (with ammonia or a different amine) as desired. in these and other ways known to those skilled in the art N-(dialkylamino aryl) amides of itaconic acid may be readily formed.

For reasons of economy and ease of preparation, the methyl and ethyl esters of N-(p-dimethylamino phenyl) itaconic amide acid are usually preferred when an ester is used as illustrated by the following formula NHCaH N(C H3)2 OHzCO in which R is a methyl or ethyl group. These esters are prepared simply by refluxing methanol or ethanol with itaconic acid in the presence of small amounts of an esterification catalystsuch as sulfuric acid, toluene sulfonic acid, cation-exchange resins containing sulfonic acid groups, etc....,to formtheacid .esterwhich is then .converted to the acid chloride by refluxing with thionyl chloride and thereafterreacted with p-arnino dimethyl aniline .to produce the methyl or ethyl ester of N-(p-dimethylamino phenyl) itaconic amide acid. Alternatively, the'N-(pdirnethylamino phenyl) itaconic amide acid Iitself iscfone.

veniently prepared by reacting itaconic anhydride or itaconic acid chloride with the amino dlimethyl aniline. The acid chloride and anhydride are sufficiently reactive to form the amide merely upon mixing at room temperature. In some cases where the anhydride or acid chloride,

are not as reactive or in order to get more complete reaction gentle heating may be advantageous. This amideacid can be readily converted to a sodium or potassium salt and esterified with dimethyl or diethyl sulfate to the corresponding ester.

methyl-cyclopentyl,

3 I The proportions of the amide in the polymerization products of the invention may vary over a wide range, ranging from all or substantially all amide down to very small amounts of amide such as may be employed in acrylonitrile polymers to impart dye susceptibility there to. Although even smaller amounts are somewhat effective, the improvement in susceptibility of acrylonitrile copolymers to dyes becomes particularly noticeable when the amide content of the copolymer is about 0.1 per cent and the susceptibility increases as the amount of amide is increased. Ordinarily sufficient improvement in dye susceptibility is obtained with amounts of amide ranging up to about or per cent but it may be advantageous for reasons such as in the preparation of ion-exchange polymers or additives to improve dyeing properties to.

have a major proportion of amide in the acrylonitrile copolymer. In such cases the concentration of amide may range up to or approaching 100 per cent. Within these proportions acrylonitrile copolymers of the invention show great affinity toward many dyes especially basic, acidic, vat, and cellulose acetate dyes.

In addition to the improvements eifected in the resulting copolymers, the use of N-(dialkylamino aryl) itaconic acid amides has certain other advantages over the use of the corresponding acids. For example, the amides are more soluble in acrylonitrile than the acids. Therefore it is generally easier to get complete copolymerization of the amide with acrylonitrile in solution, emulsion and suspension polymerizations. Still further advantages accrue from the presence of these amides. Thus when nonesterified monoamides are used the copolymers of the invention show high susceptibility to basic dyes.

The acrylonitrile copolymers discussed herein are soluble in N,N-dimethyl acetamide (DMA), N,N-dimethyl formamide (DMF), butyrolactone, ethylene carbonate, N,N-dimethyl methyl urethane of the formula CH3 2NCOOCH3 ethylene carbamate, N-methyl-2-pyrrolidone, and a number of similar solvents, used alone or in conjunction with N,N-dimethyl cyanamide, N,N-dimethyl cyano-acetamide, N,N-dimethyl methoxy-acetamide, methylene dinitrile, methylene dithiocyanate, formyl caprolactam, formyl morpholine, tetramethylene sulfone, etc. Nitroalkanes, such as nitromethane, may be used as solvents for such copolymers having no more than about 85 per cent acrylonitrile, providing the comonomers used in preparing such copolymers do not have substituent groups of equal or greater secondary bonding force than the cyano groups in acrylonitrile. Copolymers of the present invention which have high proportions of monomers of relatively low secondary-valence bonding strength, such as vinyl chloride, may often be dissolved in acetone or mixtures of acetone and solvents of the above types.

This invention will be more fully described by the following examples which illustrate methods of practicing the invention. In these examples and throughout the specification, parts and percentages are intended to mean parts by weight and percentages by weight.

Example I Five polymers of acrylonitrile are prepared from the following monomer compositions:

N-( p-dirfiethyg ammop eny Polymer Acrylomtrlle itaconic amide acid Parts Parts mer is dissolved in N,N-dimethyl acetamide or butyrolactone and a film cast from each solution.

A water solution of methylene blue dye (a basic dye) is prepared by making a paste of the dye and then diluting to a 1 per cent by weight dye solution. This dye solution is kept boiling for one hour while the aforementioned films are immersed therein for one hour. The dyed films are then removed and separately subjected to washing with boiling water for one hour, the boiling water being changed frequently to remove the desorbed dye. The unmodified polyacrylonitrile film shows only a light tint, Whereas the mono-N-(p-dimethyl-amino phenyl) itaconic amide acid copolymers are a deep and dense shade. Identical films, cold-drawn and heat-treated, show dyeing characteristics similar to the undrawn films.

Fibers are spun from the same N,N-dimethyl acetamide or butyrolactone solutions either by dry spinning or by wet spinning, into glycerine baths. The fibers are substantially freed from solvent and dried. After cold-drawing the dried fibers 600-900 per cent at 120-145 C. and subsequently heat-treating them at 150 C. for one hour, the fibers are given the same dyeing and washing treatment described above with the same results as for the films a light tint being acquired by the unmodified polyacrylonitrile fibers and a deep and dense color being given to the itaconate copolymer fibers.

Instead of N-(p-dimethylamino phenyl) itaconic amide acid, the various N-(dialkylamino aryl) itaconic amide acids disclosed above may be used.

Example II Five polymers of acrylonitrile are prepared from the following monomer compositions:

Monomethyl ester of N-(p-dimethyl- Polymer Acrylonitrile amino phenyl) itaconic amide acid Parts Parts To 900 partsof water, adjusted to a pH of about three, in a suitable reactor, is added 0.5 to 1 part sodium dodecyl benzene sulfonate, 1.0 part of ammonium persulfate, 0.5 part of sodium bisulfite, and parts of monomer or monomer mixture. oxygenated nitrogen and heated with agitation to 50 C.. for 24 hours. Steam is introduced into the reactor to remove unpolymerized monomers from the mixture. A small amount of aluminum sulfate is added to the mixture and the polymer isolated by filtration.

The polymer is then washed with water and with methyl alcohol. A portion of the polymer is dissolved in dimethyl formamide or butyrolactone and a film cast from the solution. The film is washed entirely free of solvent and stretched at a ratio of about 8:1 in a glycerine bath at to C. The film is then washed in water and dyed in a bath containing for each part of film 0.05 part of 1,5-diamino-4,S-dihydroxyanthraquinone-3-sulfonic acid, 0.03 part sulfuric acid and 50 parts water (50:1 bath-film ratio) at boiling temperature for one hour. The film is then removed and washed with water and scoured for 15 minutes in a 0.4 per cent soap solution at 85 C. Whereas the unmodified polyacrylonitrile when treated in this manner has little or no color, all of the copolymers are dyed to a deeper blue shade.

Fibers are spun from the same solutions either by dry spinning, or by wet spinning. The fibers are substantially freed from solvent and dried. After cold-drawing the dried fibers 600-900 per cent at 120-145 C. and subsequently heat-treating them at 'C. for one hour, the fibers are given the same dyeing and washing treatment described above with the same results as for the films, a light tint being acquired by the unmodified polyacrylonitrile fibers and a deep and dense color being given to the copolymer fibers. The polymers of this example are also soluble in dimethyl formamide, dimethyl acetamide, tetramethyl urea, butyrolactone, ethylene carbonate, formyl morpholine, etc.

The reactor is then flushed with de- Instead of the monomethyl itaconate ester amide: of the above; example, various: other esters of the. itaconic amide acid maybe. used, such. as the. ethyl, propyl, iso.-' propyl, butyl isobutyl, tertiary-butyl, hexyl, tolyl, phenyl, naphthyl, cyclopentyl, cyclohexyl', benzyl, phenethyl, etc. esters. Likewise the esters of the other N.-(dialkylamino aryl) itaconic amide acids disclosed above may be used.

Example III Five parts of the copolymer. fiber. D of Example Iv is dyed; to adeep green shade using. the vat, color dimethoxydibenzanthrone at 70 C. in a bath. containing 0.5 part of dye, 0.25 partv sodium hydroxide, 0.5 part sodium hydrosulfite and Ipartsof Water (20:1 bath-fiber ratio). After the first 1-5 minutes of heating 0.25 part of Glaubers salt is added. The sample is then. oxidized in a 0.5 per cent sodium dichromate 1.0 per cent acetic acid at 70 C. for 30 minutes in a 20:1 bath-fiber ratio. The dyed fiber is then scoured in a 05 per cent boiling soap solution. A sample of yarn prepared from the unmodified polyacrylonitrile and dyed under the same conditions acquired only a light. shade of color.

If 1',5-di-p-anisoylamino-4,8 dihydroxy-anthraquinone in used as the vat dye, the copolymer' fiber is dyed a strong violet color.

Example IV The procedure of Example I is repeated. for the poly merization of the. following monomer compositions:

Sometimes copolymers D and B, when dissolved in nitromethane may have gelled", partially dissolved particles known as. fisheyes. In: such cases, the solubility may be improved by the addition of small amounts of materials which are good solvents foracrylonitrile polymers, such. as butyrolactone, ethylene carbonate, dimethyl formamide, dimethyl acetamide, tetrame'thyl urea, etc. In addition, certain materials. which are relatively poor solvents for polyacrylonitrile, such as diethyl formamide, diethyl acetamide, diethyl propionamide, etc., may be added to improve the solubility; Also, when acetone r solutions of copolymer F contain gelled particles; clar1fication of the solution may be effected by the. addition of nitromethane, diethylformamide, diethyl acetamide, etc.

Dyeing tests of these copolymers show improvements in dyeing susceptibility similar to those of Example I. The procedure. of this-example may also be used with the various other monoesters setforth above.

Example V The. procedure of, Example I is repeated for t he polymerization of. the. following monomer compositions:

Dyeing tests of these copolymers'show improvements in dye susceptibility similar to Example I. In place of styrene, various SiYI'fillfidfiFiVQfiVfiS may' be used, such as a-lphamethyLstyre-rie; nuclear-substituted chloro.-styrenes,, i. e., orthoa, meta-,-. and? para-chloroz-styrenen d1chloro-- Example VI The procedure of Example I is repeated for the polymerization of. the following. monomer compositions:

I 5 Methyl gsiter Acrylo- Vlnylldene, O l Oopolymer Soluble. Polymer v .methylamlno 2 nitrlle I Chloilde tolyn itaconic I In amide acid i Pt. Pt. Pt. A 85 5 l0 DMF, DMA, etc. B 65 I0 DMF, DMA, etc. 45 45 10 DMF, DMA, etc. D 25 65. 10 DMF, DM-A, etc. 5 85 10 DMF, DMA, etc;

With. the above vinylidene chloride copolymers and similar copolymers having a total of aerylonitrile and vinylidene chloride of at least. 85.- per cent in the polymer molecules, only the more active solvents, such. as butyrolactone, ethylene carbonate, N,N-dimethyl acetamide, N,N-dimethyl formamide, N,N,N',N-tetramethy1 urea, etc'., can be used. as solvents. The above copolymers dye more readily and thoroughly than similar copolymers con taining no methyl ester of N-(dimethylamino phenyl) itaconic amide acid.

The procedure of this example may also be used with the various other monoesters set forth above.

Example VII The procedure of Example I is repeated for the polymerization of the following monomer compositions:

Methyl ester A 1 v in vm 1 ili l i cry 0.- inyl ene y .me yam no nitrile Chloride Chloride phenyl) itaconic amide acid Pt. Pt. Pt. Pl. A 80 10 8 2 2O 8 2 7O 15 13 2 5O 20 28 2 20 18 60 2 The dyeing tests of the copolymer products show dye susceptibility similar to the copolymers of Example I.

The procedure of this example may also be used with the various other monoesters set forth above.

Instead of copolymerizing the amides with the acrylonitrile,theN-(dialkylamino aryl.) itaconic amides may be polymerized.independently to produce polymers, and the prepared polymer used to modify polyacrylonitrile or other .acrylonitrile. copolymers. Thev acrylonitrile. polymers. maybe blended withv up to 10. per cent. or more of the. polyN- (fp.-dimethylamino phenyl) itaconic acid amide. without serious. loss in the physical and chemical properties of the: resulting dyedj structures. The. following. example is. illustrative.

Example. VIII acid-is preparedsubstantially in: accordance with. the pro cedure of; Example: I1

polymer is preparedindimethyl formamide and added to agdirnethylformamide: solution of polyacrylonitrile, containing 20-per.- cent polymer, so that a composition con A. 10.. per cent-solution of? this:

sisting of .90. parts. of ,pollyacrylonitrile and 10 .parts. .of.

the amide is "obtained. The solution is heated to 130 c.

after which the solution is filtered. Films and fibers prepared from this mixture are dyed in accordance with the process of Example I, and satisfactory dyed, shaped articles are obtained. The unmodified polyacrylonitrile without the addition of the itaconic amide showed little or no dye retention.

Instead of using a homopolymer of N-(dialkylamino aryl) itaconic acid amide, copolymers of the itaconic amide, such as Polymers D and E of Example II, may be used as modifiers for the unmodified homopolymers of acrylonitrile. For example, Polymer E of Example II, which consists of 80 parts of acrylonitrile and 20 parts of methyl ester of N-(p-dimethylamino phenyl) itaconic amide acid, has excellent compatibility with homopolymers of acrylonitrile. In many cases, it is desirable to use the copolymers of the N-(dialkylamino aryl)-type itaconic acid amides, which have even a higher ratio of the itaconic amide, as for example, 50 to 70 parts of the itaconic amide copolymerized with acrylonitrile or methacrylonitrile. In other cases, the copolymers of itaconic amides with other monomers are satisfactory such as, for example, copolymers of styrene, vinyl chloride, vinylidene chloride, alpha-methyl-styrene, etc.

When it is desired to modify an acrylonitrile copolymer such as the copolymer of acrylonitrile ,and styrene or the copolymers of acrylonitrile and other copolymerizable ethylenic compounds, it is usually desirable to use as modifiers copolymers containing at least one structural unit present in the acrylonitrile copolymer. Thus as there are present in the acrylonitrile copolymer, structural units derived from the acrylonitrile and styrene, it is desirable to have present in the modifying copolymer structural units derived from styrene and/ or acrylonitrile, advantageously both, in addition to those derived from the amide. By thus including in the modifying copolymers structural units of the same type as the structural units of the copolymer to be modified, greater compatibility between the acrylonitrile copolymer to be modified and the modifying copolymer is obtained and the two are more readily soluble in the mutual solvent and will more readily mix into homogeneous polymer mixtures.

.The di-N-(dialkylamino aryl) itaconic amides of the structure in which A, R and R" are as indicated above may be used instead of the monoamide in the practice of this invention.

The polymerization products of the present invention have in the polymer molecule a plurality of repeating units of the formula v Cz [to in which Y and Z are as indicated above and will contain additional repeating units of the formula CH2CH when the amide is copolymerized with acrylonitrile.

4 In addition, the polymerization products may contain any number of repeating units of the type obtained by the copolymerization-of N-(dialkylarnino aryl) itaconic acid amide, or a mixture of acrylonitrile and amide, with one. or more copolymerizable ethylenic compounds, such amide-units may contain various proportions of such- X-ray diffraction patterns.

monomer units as obtained from vinylidene chloride, methacrylonitrile, fumaronitrile, and beta-cyano-acryl amide without considerable reduction in solvent resistance. Replacement of acrylonitrile units in the copolymers by vinyl chloride, styrene and alpha-methyl-styrene units result in copolymers of lowered solvent resistance, the amount of such lowering in resistance in each case depending on the amount substituted. In addition to the solvent resistance, certain other physical properties of the copolymers are aifected by the presence of these additional units in the copolymers; The amount and character of the changes in physical properties of these copolymers depend again on the type and proportion of copolymerizing monomer or monomers used. For example, the tensile strength of an acrylonitrile N-(dialkylamino aryl) itaconic amide type copolymer will decrease much more when a monomer having relatively weak secondary bonding forces, such as styrene or ethylene is used to replace part of the acrylonitrile than when one or more monomers having relatively strong bonding forces, such as methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, methyl beta-cyano-acrylate and vinylidene chloride, is used to replace part of the acrylonitrile., Moreover, the ability of these copolymers to form molecularly oriented shaped articles depends on the type and amount of the copolymerilzing monomer or monomers used to'replace acrylonitri e.

Other copolymerizable ethylenic compounds, which may also be present in the polymerizable masses for copolymerization with the N-(dialkylamino aryl) itaconic amides include one or more of the following: acrylates, e. g. methyl acrylate; methacrylates, e. g. methyl methacrylate; acrylamides, methacrylarnides; vinyl esters, such as vinyl acetate; maleates, such as dimethyl and diethyl maleates; fumarates, such as dimethyl and diethyl fumarates; itaconic diesters, such as dimethyl and diethyl itaconates;

itaconamide; vinyl halides, such as vinyl fluoride, vinyli-.

dene fluoride, tetrafluoroethylene, trifluorochloroethylene; vinyl aryls, such as vinyl naphthalenes and substituted styrenes as listed in Example V, etc.

The polymerization products of this invention may be prepared by various polymerization systems, such as emulsion, suspension, mass and solution polymerizations. In addition to the monomers, the polymerizable mass may also contain other materials such as catalysts, e. g. peroxides, such as benzoyl peroxide, naphthyl peroxides, phthalyl peroxide, tertiarybutyl hydroperoxide, hydrogen peroxide, cyclohexyl hydroperoxide, tertiary-butyl perbenzoate,-

etc., azo catalysts, persulfates, such as ammonium persulfate, etc., solvents, suspension or emulsion media, emulsifying agents, suspension agents, plasticizers, lubricants,-

etc.

For use in the preparation of shaped articles, the polymerization products of this invention have molecular weights preferably of at least about 10,000. However,

polymerization products of molecular weights less than 10,000 may be used for other purposes, such as impregnants, solvent resistant coatings, etc. The molecular weight of the polymerization products is dependent on the concentrations of the monomers, the amount and for points of crystallization and dark areas for the non crystalline regions. The intensity or number of these bright spots increases with the degree of orientation or crystallization. Amorphous or non-crystalline materials give X-ray diagrams having very few high lights or bright spots whereas crystalline or oriented materials give definite definite relationships of the bright spots with regard to posititon and spacing which are generally characteristic of the composititon of the material being X-rayed. In fibers or films the orientation usually follows the direction of drawing or stretching so that the orientation is parallel to as in the preparation of viscose rayon. In wet spi nn ing,1

In "these patterns there are orientation. articles of particular usefulness are prepared from copoly- .-the-solution of copolymer may be spun into a substance which 1s a non-solvent for the copolymer, but which is advantageously compatible with the solvent in which the copolymer is dissolved. For example, water, acetone,

- methyl alcohol, carbon disulfide, glycerine, chloroform,

carbon tetrachloride, benzene, etc., may be used as a precipitating bath for N,N-dimethyl acetamide, N,N,N',-

I N'-tetramethyl urea, butyrolactone, ethylene carbonate,

at substantially constant length, at about 100-160 C.

to effect further crystallization and removal of the re maining solvent. The term heat-treated, as used herein, refers to the application of heat to an object, usually at a controlled temperature and usually by means of the medium surrounding the object.

Many of the acrylonitrile copolymers of this invention may be molecularly oriented, espec1ally if there is no more than 15 percent of N-dialkylamino aryl) itaconic amide in the copolymer molecule. This is true when the major portion of the copolymer is acrylonitrile, for example, 85 percent or more acrylonitrile, or when the other copolymerizing monomers used in making such copolymers have substituent groups having secondary-valence bonding forces equal to or greater than exhibited by the cyano group in acrylonitrile. For example, if such monomers as methacrylonitrile, fumaronitrile vinylidene chloride, beta-cyano-acrylamide and methyl beta-cyanoacrylate are used with acrylonitrile and the N-(dialkylamino aryl) itaconic acid amide, the proportion of acrylonitrile in the copolymers may be much less than 85 percent without destroying the capacity for molecular Molecularly oriented, cold-drawn, shaped mer compositions containing in the polymer molecules 60-99.9 percent acrylonitrile, 0.1-15 percent, advantageously 0.1- percent, N-(dialkylamino aryl) itaconic amide, with or without one or more monomers of the class consisting of vinylidene chloride, vinyl chloride, styrene, alpha-methyl-styrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide and methyl beta-cyanoacrylate, the effects of the presence of the monomers of this class being noticeable when the monomer is present in the polymer molecule in amounts of one percent or more.

The polymerization products of this invention show great affinity for the acetate, basic, acidic and vat dyes. The cellulose acetate dyes which are effective with these polymerization products are mainly amino-anthraquinone derivatives. The basic dyestuffs toward which these polymerization products show great affinity are preferably those which contain amido, alkylamido, or ammonium groups, such as NH2, -N(CH3)2, N(C2H5)2, NHCsH5, -N(CH3)3OH, etc. and which may also be used in the form of their salts, i. e. the hydrochlorides, sulfates or oxalates. Some of these basic dyes are Methylene Blue, Rhodamine B, Indamine Blue, Auramine, Meldolas Blue, Chrysoidine Y, Acridine Yellow, Magenta, Crystal Violet, Thioflavine T, Saifranine and Bismarck Brown. The cellulose acetate dyes which are effective with these polymerization products are mainly amino-anthraquinone derivatives, basic azo compounds and other basic substances, such as the Duranol, Dispersol, Sericol, etc. dyestuffs. A number of other acidic dyes that can be used are anthranilic acid 1-(4-sulfo phenyl), 3-methyl-5-pyrazolone; 1,5-diamino-4,8-dihydroxyanthraquinone-3-sulfonic acid; l-aminonaphthalene- 4-sulfonic acidalpha-naphthol-4-sulfonic acid; the sodium salt of sulfanilic acid aniline- Z-benzoyl-amino-S- naphthol-7-sulfonic acid; the sodium salt of 4,4'-diaminostilbene-2,2'-di-sulfonic acid3(pheno1)z ethylated; 1,5- diamino-4,8-dihydroxyanthraquinone-3-sulfonic acid; dye prepared by diazotizing 1-aminonaphthalene-4-sulfonic acid and coupled with alpha-naphthol-4-sulfonic acid; the sodium salt of (m-aminobenzoic acido-anisidene) phosgenated; the sodium salt of (2-naphthol-6,8- disulfonic acid benzidine phenol)ethylated; dimethoxydibenzanthrone; and 1,5-di-p-anisoylamino-4,8-dihydroxyanthraquinone.

From the molecularly orientahle copolymers of this invention fibers may be prepared having improved dyeing properties, low shrinkage in boiling water, sometimes as low as 3 to 5 percent or less of the cold-drawn or stretched article, good heat resistance, and tensile strength in the order of 4 to 6 grams per denier. Moreover, these properties make the fibers desirable in the manufacture of hosiery and for such all-purpose fabrics as used for blouses, shirts, suits, etc.

I claim:

-1-. The polymerization product having repeating acid reaction groups obtained by polymerizing a mass comprising an N-(dialkylamino benzenoid hydrocarbon aryl) itaconic acid amide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms.

2. The composition of claim 1 in which the mass also contains a polymerizable ethylenic compound selected from the class consistingof acrylonitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methyhstyren, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, and methyl beta-cyano-acrylate.

3. The polymerization product having repeating acid reactive groups obtained by polymerizing a mass comprising acrylonitrile and an N-(dialkylamino benzenoid hydrocarbon aryl) itaconic acid amide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms.

4. The copolymer of claim 3 in which the amide is present in at least about 0.1 percent of the polymerizable mass.

5. A polymerization product having repeating acid reactive groups obtained by polymerizing a mass comprising an N-(dialkylamino benzenoid hydrocarbon aryl) itaconic amide acid in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms.

6. A polymerization product having repeating acid reactive groups obtained by polymerizing a mass comprising an ester of an N-dialkylamino benzenoid hydrocarbon aryl) itaconic monoamide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms.

7. A polymerization product having repeating acid reactive groups obtained by polymerizing a mass comprising the methyl ester of N-dialkylamino benzenoid hydrocarbon aryl) itaconic acid monoamide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms.

8. A polymerization product having repeating acid reactive groups obtained by polymerizing a mass comprising an N-(dialkylamino benzenoid hydrocarbon aryl) itaconic acid diamide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms.

9. A polymerization product having repeating acid reactive groups obtained by polymerizing a mass comprising N,N'-di(dialkylamino benzenoid hydrocarbon aryl) itaconic acid diamide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms.

10. A polymeric composition having in the polymer molecule a plurality of repeating acid reactive units having the formula C [to 11. The polymerization product of claim 10 which contains in the polymer molecule a plurality of repeating units of the formula the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms, said copolymer having a molecular weight of at least about 10,000 and containing in the polymer molecule no more than about 15 percent by weight of said pound selected from the class consisting of vinyl chloride,-

vinylidene chloride, styrene, alpha-methyl-styrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, and methyl beta-cyano-acrylate.

15. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about 6098.9 percent by weight acrylonitrile, about 0.1 to percent by weight N-dialkylamino benzenoid hydrocarbon aryl) itaconic acid amide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms and about 1 to 39.9 percent by weight vinylidene chloride.

16. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about 60-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weight N-(dialkylamino benzenoid hydrocarbon aryl) itaconic acid amide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atcclams and about 1 to 39.9 percent by weight vinyl chlorl e.

17. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about 60-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weight N-(dialkylamino benzenoid hydrocarbon aryl) itaconic acid amide in which the alkyl groups contain not more than 3 carbon atoms each and aryl group contains not more than 14 carbon atoms and about 1 to 39.9 percent by weight styrene.

18. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about -989 percent by weight acrylonitrile, about 0.1 to 5 percent by weight an amide having the following formula and about 1 to 39.9 percent by weight of a compound selected from the class consisting of vinyl chloride, vinylidene chloride, styrene, alpha-methyl-styrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, and methyl beta-cyano-acrylate.

19. A polymerization product having acid reactive groups obtained by polymerizing a mass comprising N- (p-dimethylamino pheny1)itaconamic acid.

20. The polymerization product having acid reactive groups obtained by polymerizing a mass comprising acr lonitrile and N-(p-dimethylamino phenyl) itaconamic aci Fieser et al.: Organic Chemistry (D. C. Health and Co.; Boston; 1944), page 32. 

1. THE POLYMERIZATION PRODUCT HAVING REPEATING ACID REACTION GROUPS, OBTAINED BY POLYMERIZING A MASS COMPRISING AN N-(DIALKYLAMINO BENZENOID HYDROCARBON ARYL) ITACONIC ACID AMIDE IN WHICH THE ALKYL GROUPS CONTAIN NOT MORE THAN 3 CARBON ATOMS EACH AND ARYL GROUP CONTAINS NOT MORE THAN 14 CARBON ATOMS. 